Thioindigo vat dye.



SIGNORS TO rannwnni'rn' vo'ma. lanterns} wows"eenemas: or nccnsr ena THEMA'IN, GERMANY, A oonron'a'rron or GERMANY.

THIOINDIGO YAT No Drawing.

To all whom'it may concern:

Be it known that we, A. LBRECHT Somtm'r, Ph. 1)., chemist, and KARL Tnmss, Ph. D., chemist, citizens of the Empire of Germany, residing'ut HtSchst-on-the-Main, Germany, have invented certain new andusetul Imirovements in the Manufacture of New Vat yestufls, of which the following is a specification.

e have found that the polyhalogenthioindigoes, which can be obtained for in stance by treating thioindigo-dyestuifs with an'excess of hroniin or with bromin in presence of chlorosulfonic acid, are capable, when heated with rimary buses or ammonia, preferably with the addition of substances which facilitate the substitution of the halogen, for instance, in the anthraquiinstance as are produced by 'tion of 80% strength while a'cldin half 11- none series, copper, acetate of soda orthe like of part1; replacing the halogen, particu urly bromin, and thus forming new nitrogenous vat-dyestuffs.

Example I. 20 parts of pentabrom-t-hioindigo or a tetrabrom-thioi.udi o, such for ln'ominating thioindi 'o in presence of chlorosulfonic acid or hy brommating with liquid bromin, are heated for about 5 hours to about 120 with about 150 parts of an ammonia solu part of copper-powder, with or wit put the addition of some sodium acetate. After filtering and washing with water, the product is a bluish-violet powder which dyes cotton and wool violet tints of reat; fast-- ness. Ihe product thus obtained contains less bron'iin than the parent material and analysis shows that nitrogen has entered it. By heating to a higher temperature, products of a still bluer tint are obtained.

Example II. 20 parts or penta or tetrabrom-thioindigo are heated for some hours to about 150 C. or for 'a short time to boilin temperature with 60 parts of paratofuidin or anilin, with or without the addition of a solvent, such for instance as nit-robenzene, during which" operation it is ad vantageous to add one of the agents known for facilitating the replacement of a halogen by an amin, suclrfor instance RS-SOCllllnl acetate and copper-powder. The dyestufi obtained after removiu the excess of amin is in the form of a vitilet-blue powder which Wool violet-blue to blue tints. The more energetic the action of the amin has been, the deeper blue the tint will be.

Eaample III. 69 parts of pentabromthromdigo containing about 57% of'bromin 15 parts of paraphenylenediamin and 12 15 parts of sodium acetate are introduced, while stirring, into 690 parts -of'nitrobenzene and the mixture is heated for two hours to l60170 O. (oil-bath temperature) while stirring until the solution assumes a blue color. After removing the nitrob'enzene by passing steam through it, the product is in the form of a blue owder which dyes cotton and wool f ast blue tints.

I Example IV. 69 parts of pentahrom-thioindigo, 2.0 parts of alpha-naphthylami n,

1618 parts of sodium acetate and half apart of copperpowder are introduced into 690 parts of naphthalene and the mixture is heated for about 2 hours to ebullition After removing the naphthalene by passing steam through it, the product a violet powder which dyes cotton and. wool. violet tints of greatfastness.

Instead of the aforesaid amine, other amins such for instance as monoethylamin, benzylamin, para-chloranilin, para-anisidin, para-aminodiphenylamin, henzidin or the like may he used. In like manner, other polyhalogen-thioindigoes,.such for instance as brominated dichloroor tetrachloro-thioindigoes, hrominated dichloro dimethyl thioindigoes or the like may be used in lieu of the polyhrom-thioindigo.

The new dyestnfi's are violet, violet-blue or blue powders, are soluble in concentrated sulfuric acid and hot nitr0benzene with a bluish-violet to blue coloiy'a'nd are almost insoluble in alcohol, benzene and carbon tetrachlorid.

Having now pm'ticularly descrlhed our invention, what -we claim isz l. The procex of manufacturing nitrogenous vatdyestuffs of the thioindi o series, which. consists in heating polyha ogenthioindigoes with amins of the general formula It NIL, wherein R means H, aryl, or

alltyl, substantiall as described.

2. As new pro'ucts', the herein-descrihed nitrogenous vat-dyestuils of thethiomdigo series, obtainable by heating polyhalcgen thioindigoes with amins of the eneral fordyes, in the hydrosulfite-vst. cotton and mula R NK wherein means aryl, or

alkyl; being bluish-violet to blue powders,

- color, almost insoluble in'alcohol; benzene,

carbon-tetrachlorid, and dyeing cotton and wool in-the hydrosulfite vat violet-blue to blue tints of great fastness.

3. As a new product, the vat dyestufi' obtainable by heating pentnbrom-thioindigo and anilin, being a-blue owder, soluble in concentrated Sulfuric aci and hot nitroben zene with a bluishwiolet to blue color, :11"

most insoluble in alcohol, benzene and can bon-tetrachlorid, and dyeing cot-ton antI-fwool in the hydrosulfite vat violet blue tints 15 of cat fastness.

' n testimony whereof, we afiix our sigmtures in presence of two witnesses.

ALBRECHT "SCHMIDT. KARL THIESS.

WVitnesses JEAN GRUND, CARL Gntmn. 

